CN108384979B - Hybrid reinforced copper-based composite material and preparation method thereof - Google Patents

Hybrid reinforced copper-based composite material and preparation method thereof Download PDF

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CN108384979B
CN108384979B CN201810266802.5A CN201810266802A CN108384979B CN 108384979 B CN108384979 B CN 108384979B CN 201810266802 A CN201810266802 A CN 201810266802A CN 108384979 B CN108384979 B CN 108384979B
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tih
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CN108384979A (en
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肖鹏
高镧星
姜伊辉
梁淑华
邹军涛
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Xian University of Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes

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Abstract

The invention discloses a hybrid reinforced copper-based composite material, which comprises three reinforcements: CNTs, TiB2And TiC, in the composite material structure, CNTs are distributed in a layered mode, TiB2And TiC are dispersed in the copper matrix to form a composite structure with three reinforcements reinforced in a synergetic mode. The invention also discloses a preparation method of the composite material. The invention introduces TiB with small size and uniform distribution into the copper matrix between the CNTs lamination2And TiC particles increase the resistance of dislocation movement in the material deformation process, and are mutually complemented with the strengthening effect of CNTs, so that the strength of the material is improved. In the structure of the composite material, three reinforcing bodies form a synergistic reinforcing structure with alternate distribution and complementary advantages, so that the composite material has high hardness and good conductivity; the CNTs are distributed in a laminated manner with consistent orientation, and the effects of sharing matrix load and improving the toughness of the composite material are favorably exerted.

Description

Hybrid reinforced copper-based composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of copper-based composite materials, and particularly relates to a hybrid reinforced copper-based composite material and a preparation method of the hybrid reinforced copper-based composite material.
Background
The rapid development of the power electronics industry puts urgent demands on the development of high-performance copper-based composite materials. The powder metallurgy technology is adopted to introduce various reinforcements into the copper matrix, and the realization of the synergistic enhancement effect is a new way to obtain the high-performance copper-based composite material. TiB2The TiC ceramic phase has performance characteristics of high hardness, high elastic modulus and the like, so that the strength of the Cu-based composite material can be obviously improved; and the toughness of the composite material can be improved by adding high-strength CNTs into the copper matrix. In general, powder metallurgy is used to prepare copper-based composite materials, and a high-energy ball milling method is required to realize uniform dispersion distribution of reinforcements in a matrix. However, high energy ball milling introduces more of the copper matrixDefects, causing irreversible damage to the substrate conductivity; on the other hand, the intrinsic structure of CNTs is also damaged, and the enhancement effect is greatly reduced. Therefore, a new method needs to be developed, so that the distribution state of the multi-component reinforcement in the composite material is optimized, the structure of the CNTs is not damaged, and the composite material keeps high conductivity.
Disclosure of Invention
The invention aims to provide a hybrid reinforced copper-based composite material, which ensures that the copper-based composite material has good conductivity while realizing multi-component synergistic reinforcement.
Another object of the present invention is to provide a method for preparing a hybrid reinforced copper-based composite material.
The technical scheme adopted by the invention is that the hybrid reinforced copper-based composite material comprises three reinforcements: CNTs, TiB2And TiC, in the structure of composite material, CNTs are distributed in layer form, TiB2And TiC are dispersed in the copper matrix to form a composite structure with three reinforcements reinforced in a synergetic mode.
The invention is also characterized in that the method,
the composite material comprises the following components in percentage by weight: 0.05 to 0.25 wt% of TiB2The contents are as follows: 0.50-2.5 wt% and TiC content 0.22-1.08 wt%.
CNTs are added into the composite material through an external addition method; TiB2And TiC by TiH2And B4C is reacted and synthesized in situ in a Cu matrix.
The invention adopts another technical scheme that the preparation method of the hybrid reinforced copper-based composite material is implemented according to the following steps:
step 1, weighing TiH2Powder of B4C powder and Cu powder, and ball milling and mixing the powder to obtain the TiH with a flaky shape2-B4C/Cu composite powder;
measuring a CNTs dispersion liquid, adding deionized water to dilute the CNTs dispersion liquid into a CNTs suspension liquid, and performing ultrasonic oscillation to obtain the CNTs suspension liquid with uniformly dispersed system;
step 2, the TiH obtained in the step 1 is used2-B4Adding the C/Cu composite powder into the CNTs suspension, stirring and mixing, stopping stirring when the upper layer solution is changed from black to transparent, standing, precipitating, and then drying the precipitate in vacuum to obtain CNTs-TiH2-B4C/Cu composite powder;
step 3, the CNTs-TiH obtained in the step 22-B4Filling the C/Cu composite powder into a steel die, and performing cold pressing to form a blank;
step 4, placing the pressed blank obtained in the step 3 into a graphite mold, and placing the graphite mold into an atmosphere hot pressing furnace for pressure sintering to obtain the CNTs-TiB2-a TiC/Cu composite.
The invention is also characterized in that the method,
TiH in step 12Powder B4The dosage of the C powder and the Cu powder is that TiB is generated in the composite material through in-situ reaction2: 0.50-2.5 wt%, TiC: weighing the target content of 0.22-1.08 wt%.
The parameters of the ball milling process are as follows: the ball milling time is 6-10 h, the ball-material ratio is 10: 1-20: 1, the rotating speed is 300-400 rpm, the addition amount of the process control agent absolute ethyl alcohol is 6-10% of the total mass of the powder, and the protective atmosphere is Ar.
The concentration of the CNTs suspension in the step 1 is 0.22-0.73 mg/ml; the ultrasonic oscillation time is 60-140 min, and the power is 40-60W.
In step 2, TiH2-B4The mass-volume ratio of the C/Cu composite powder to the CNTs suspension is 0.29-0.44 g/ml.
In the step 2, the vacuum drying temperature is 60-80 ℃, the vacuum degree is-0.06-0.05 MPa, and the drying time is 12-24 h; in the step 3, the pressing pressure is 300-400 Mpa, and the pressure maintaining time is 20-40 s.
And 4, pressurizing and sintering, specifically: in N2Under the protection of atmosphere, heating to 940-1060 ℃ at the heating rate of 10-20 ℃/min, then preserving heat for 40-80 min, increasing the pressure loaded on the pressed blank to 20-30 MPa in the heat preservation process, and then keeping the pressure unchanged.
The invention has the beneficial effects that the CNTs-TiB of the invention2Method for preparing a TiC/Cu composite by introducing rules into the copper matrix between the layers of CNTsVery small and evenly distributed TiB2And TiC particles increase the resistance of dislocation movement in the material deformation process, and complement the strengthening effect of the CNTs, so that the strength of the material is greatly improved, and the method for controlling the distribution mode of the CNTs and realizing multi-component powder compounding is provided. CNTs and TiB in composite material tissue2The TiC three reinforcements form a synergistic reinforced structure with alternate distribution and complementary advantages, and a composite material with high hardness and good electric conductivity is obtained; the CNTs are in laminated distribution with consistent orientation, and compared with a uniform and disordered distribution mode, the distribution is more beneficial to exerting the effects of sharing matrix load and improving the toughness of the composite material.
Drawings
FIG. 1 is a process flow diagram of the manufacturing process of the present invention;
FIG. 2 is TiH prepared in example 5 of the present invention2-B4SEM photograph of the C/Cu composite powder;
FIG. 3 shows CNTs-TiB prepared in example 5 of the present invention2-SEM photograph of the TiC/Cu composite structure;
FIG. 4 is the CNTs-TiB of FIG. 32SEM pictures of CNTs distributed in the structure of TiC/Cu composite.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a hybrid reinforced copper-based composite material, which comprises three reinforcements: CNTs, TiB2And TiC, wherein the CNTs content is as follows: 0.05 to 0.25 wt% of TiB2The contents are as follows: 0.50-2.5 wt% and TiC content 0.22-1.08 wt%. CNTs are added to the composite by an external addition method, while TiB2And TiC is made by using TiH2And B4C is reacted and synthesized in situ in a Cu matrix. In the structure of the composite material, CNTs are distributed in a layered mode, and TiB2And TiC are dispersed in the copper matrix to form a composite structure with three reinforcements reinforced in a synergetic mode.
The preparation method of the hybrid reinforced copper-based composite material is specifically implemented according to the following steps as shown in fig. 1:
step 1, preparing TiH2-B4C/Cu composite powder:
firstly, TiB is generated in the composite material through in-situ reaction2: 0.50-2.5 wt%, TiC: weighing Cu powder and TiH respectively at target content of 0.22-1.08 wt%2Powder B4C, ball-milling and mixing the three powders to obtain the TiH with a flaky shape2-B4C/Cu composite powder.
The parameters of the ball milling process are as follows: the ball milling time is 6-10 h, the ball-material ratio is 10: 1-20: 1, the rotating speed is 300-400 rpm, the addition amount of the process control agent (absolute ethyl alcohol) is 6-10% of the total mass of the powder, and the protective atmosphere is Ar.
Step 2, pretreating the CNTs dispersion liquid:
measuring a CNTs dispersion according to the content of 0.05-0.25 wt% of the CNTs in the composite material, and adding deionized water for dilution to obtain a suspension with the concentration of 0.22-0.73 mg/ml of the CNTs; and (3) carrying out ultrasonic oscillation on the CNTs suspension for 60-140 min at the power of 40-60W to obtain a uniform CNTs dispersion system.
Step 3, preparing CNTs-TiH2-B4C/Cu composite powder:
firstly, TiH prepared in step 12-B4Mixing the C/Cu composite powder with the CNTs suspension prepared in the step 2 according to the proportion of 0.29-0.44 g/ml; then stirring, stopping stirring when the upper layer solution is changed from black to transparent, standing, precipitating, and vacuum drying the precipitate to obtain CNTs-TiH2-B4C/Cu composite powder.
The vacuum drying temperature is 60-80 ℃, the vacuum degree is-0.06-0.05 MPa, and the drying time is 12-24 h.
In the stirring and mixing process, the CNTs are transferred from the suspension and adsorbed to the surface of the composite powder, and when the suspension is changed from black to transparent, the adsorption process is finished; TiH with CNTs adsorbed2-B4The C/Cu powder settled at the bottom of the beaker.
Step 4, CNTs-TiH2-B4C/Cu composite powder cold press molding:
subjecting the product obtained in step 3 toCNTs-TiH2-B4And (3) filling the C/Cu composite powder into a steel die, and cold-pressing the C/Cu composite powder into a blank, wherein the pressing pressure is 300-400 Mpa, and the pressure maintaining time is 20-40 s.
Step 5, sintering the CNTs-TiB in a hot pressing manner2-TiC/Cu composite:
and (4) putting the pressed blank obtained in the step (4) into a graphite die, putting the graphite die into an atmosphere hot pressing furnace, and performing pressure sintering, wherein the method specifically comprises the following steps: in N2Under the protection of atmosphere, the temperature is raised to 940-1060 ℃ at the temperature rise rate of 10-20 ℃/min, and then the temperature is kept for 40-80 min. And increasing the pressure loaded on the sample to 20-30 MPa in the heat preservation process, and then keeping the pressure unchanged. Stopping heating and pressurizing after heat preservation is finished, and obtaining the CNTs-TiB after the CNTs-TiB is cooled to room temperature along with the furnace2-a TiC/Cu composite.
The invention CNTs-TiB2The preparation method of the-TiC/Cu composite material is to introduce TiB with small size and uniform distribution into a copper matrix between the CNTs lamination2And TiC particles increase the resistance of dislocation movement in the material deformation process, and complement the strengthening effect of the CNTs, so that the strength of the material is greatly improved, and the method for controlling the distribution mode of the CNTs and realizing multi-component powder compounding is provided. CNTs and TiB in composite material tissue2The TiC three reinforcements form a synergistic reinforced structure with alternate distribution and complementary advantages, and a composite material with high hardness and good electric conductivity is obtained; the CNTs are in laminated distribution with consistent orientation, and compared with a uniform and disordered distribution mode, the distribution is more beneficial to exerting the effects of sharing matrix load and improving the toughness of the composite material.
Example 1
According to the generation of TiB in the composite material by in situ reaction2: 0.5 wt%, TiC: cu powder and TiH powder were weighed to a target content of 0.22 wt%2Powder B4And C, powder. And then the three powders are added into a stainless steel ball milling tank for ball milling. The ball milling process adopts: the ball-material ratio is 10:1, the ball milling time is 6h, the rotating speed is 350rpm, the protective atmosphere is Ar, the process control agent is absolute ethyl alcohol, and the addition amount is 6 percent of the total mass of the powder.
Measuring a CNTs dispersion liquid according to the content of 0.25 wt% of CNTs in the composite material, and adding deionized water for dilution to obtain a CNTs suspension liquid with the concentration of 0.73 mg/ml; and then ultrasonically oscillating the CNTs suspension, wherein the ultrasonic process adopts the following steps: power 60W, time 140 min.
Mix TiH2-B4Mixing the C/Cu composite powder and the CNTs suspension according to the proportion of 0.29g/ml, stirring, and stopping stirring when the upper layer solution is changed from black to transparent; standing, precipitating, pouring out the upper layer liquid, and vacuum drying the precipitate to obtain CNTs-TiH2-B4C/Cu composite powder. The vacuum drying temperature is 80 ℃, the vacuum degree is-0.05 MPa, and the drying time is 12 h.
CNTs-TiH2-B4C/Cu composite powder is filled into a steel mould for cold pressing and molding, the pressing pressure is 300MPa, and the pressure maintaining time is 20 s; putting the pressed compact into a graphite die for hot-pressing sintering, wherein the sintering process comprises the following steps: heating to 700 ℃ at a heating rate of 20 ℃/min, heating to 940 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 20MPa for 40min, and furnace-cooling to obtain CNTs-TiB2-a TiC/Cu composite. The hardness was 108HBW and the conductivity was 51.72% IACS.
Example 2
According to the generation of TiB in the composite material by in situ reaction2: 2.5 wt%, TiC: weighing Cu powder and TiH respectively at target content of 1.08 wt%2Powder B4And C, powder. And then the three powders are added into a stainless steel ball milling tank for ball milling. The ball milling process adopts: the ball-material ratio is 18:1, the ball milling time is 10h, the rotating speed is 370rpm, the protective atmosphere is Ar, the process control agent is absolute ethyl alcohol, and the adding amount is 10 percent of the total mass of the powder.
Measuring a CNTs dispersion liquid according to the content of 0.05 wt% of CNTs in the composite material, and adding deionized water for dilution to obtain a CNTs suspension liquid with the concentration of 0.22 mg/ml; and then ultrasonically oscillating the CNTs suspension, wherein the ultrasonic process adopts the following steps: the power is 40W, and the time is 60 min.
Mix TiH2-B4Mixing and stirring the C/Cu composite powder and the CNTs suspension according to the proportion of 0.44g/ml, and stopping stirring when the upper layer solution is changed from black to transparent; standing, precipitating, pouring out the upper layer liquid, and precipitatingThe sediment is dried in vacuum to obtain CNTs-TiH2-B4C/Cu composite powder. The vacuum drying temperature is 60 ℃, the vacuum degree is-0.06 MPa, and the drying time is 21 h.
CNTs-TiH2-B4C/Cu composite powder is filled into a steel die for cold press molding, the pressing pressure is 370MPa, and the pressure maintaining time is 40 s; putting the pressed compact into a graphite die for hot-pressing sintering, wherein the sintering process comprises the following steps: heating to 750 ℃ at a heating rate of 20 ℃/min, heating to 970 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 80min under the pressure of 30MPa, and cooling along with the furnace to obtain CNTs-TiB2-a TiC/Cu composite. The hardness was 138HBW and the conductivity 54.8% IACS.
Example 3
According to the generation of TiB in the composite material by in situ reaction2: 1.5 wt%, TiC: cu powder and TiH powder were weighed to a target content of 0.65 wt%2Powder B4And C, powder. And then the three powders are added into a stainless steel ball milling tank for ball milling. The ball milling process adopts: the ball-material ratio is 15:1, the ball milling time is 9h, the rotating speed is 300rpm, the protective atmosphere is Ar, the process control agent is absolute ethyl alcohol, and the addition amount is 7 percent of the total mass of the powder.
Measuring a CNTs dispersion liquid according to the content of 0.15 wt% of CNTs in the composite material, and adding deionized water for dilution to obtain a CNTs suspension liquid with the concentration of 0.53 mg/ml; and then ultrasonically oscillating the CNTs suspension, wherein the ultrasonic process adopts the following steps: power 55W, time 100 min.
Mix TiH2-B4Mixing the C/Cu composite powder and the CNTs suspension according to the proportion of 0.35g/ml, stirring, and stopping stirring when the upper layer solution is changed from black to transparent; standing, precipitating, pouring out the upper layer liquid, and vacuum drying the precipitate to obtain CNTs-TiH2-B4C/Cu composite powder. The vacuum drying temperature is 70 ℃, the vacuum degree is-0.055 MPa, and the drying time is 18 h.
CNTs-TiH2-B4C/Cu composite powder is filled into a steel die for cold pressing and molding, the pressing pressure is 330MPa, and the pressure maintaining time is 25 s; putting the pressed compact into a graphite die for hot-pressing sintering, wherein the sintering process comprises the following steps: firstly heating up to 800 ℃ at a heating rate of 15 ℃/min, and then changing the temperature to 10 ℃The temperature rise rate of min is increased to 1030 ℃, the temperature is kept for 50min under the pressure of 25MPa, and the CNTs-TiB is obtained after furnace cooling2-a TiC/Cu composite. The hardness was 112HBW and the conductivity was 49.51% IACS.
Example 4
According to the generation of TiB in the composite material by in situ reaction2: 2.0 wt%, TiC: cu powder and TiH powder were weighed at a target content of 0.86 wt%2Powder B4And C, powder. And then the three powders are added into a stainless steel ball milling tank for ball milling. The ball milling process adopts: the ball-material ratio is 13:1, the ball milling time is 7h, the rotating speed is 330rpm, the protective atmosphere is Ar, the process control agent is absolute ethyl alcohol, and the adding amount is 9 percent of the total mass of the powder.
Measuring a CNTs dispersion liquid according to the content of 0.1 wt% of CNTs in the composite material, and adding deionized water for dilution to obtain a CNTs suspension liquid with the concentration of 0.39 mg/ml; and then ultrasonically oscillating the CNTs suspension, wherein the ultrasonic process adopts the following steps: the power is 45W, and the time is 80 min.
Mix TiH2-B4Mixing the C/Cu composite powder and the CNTs suspension according to the proportion of 0.39g/ml, stirring, and stopping stirring when the upper layer solution is changed from black to transparent; standing, precipitating, pouring out the upper layer liquid, and vacuum drying the precipitate to obtain CNTs-TiH2-B4C/Cu composite powder. The vacuum drying temperature is 65 ℃, the vacuum degree is-0.05 MPa, and the drying time is 15 h.
CNTs-TiH2-B4C/Cu composite powder is filled into a steel mould for cold pressing and molding, the pressing pressure is 350MPa, and the pressure maintaining time is 35 s; putting the pressed compact into a graphite die for hot-pressing sintering, wherein the sintering process comprises the following steps: heating to 800 ℃ at a heating rate of 15 ℃/min, heating to 1000 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 23MPa for 70min, and furnace-cooling to obtain CNTs-TiB2-a TiC/Cu composite. The hardness was 123HBW and the conductivity was 53.22% IACS.
Example 5
According to the generation of TiB in the composite material by in situ reaction2: 1.0 wt%, TiC: cu powder and TiH were weighed to a target content of 0.43 wt%2Powder B4C powder. And then the three powders are added into a stainless steel ball milling tank for ball milling. The ball milling process adopts: the ball-material ratio is 20:1, the ball milling time is 8h, the rotating speed is 400rpm, the protective atmosphere is Ar, the process control agent is absolute ethyl alcohol, and the addition amount is 8 percent of the total mass of the powder.
Measuring a CNTs dispersion liquid according to the content of 0.2 wt% of CNTs in the composite material, and adding deionized water for dilution to obtain a CNTs suspension liquid with the concentration of 0.64 mg/ml; and then ultrasonically oscillating the CNTs suspension, wherein the ultrasonic process adopts the following steps: the power is 50W, and the time is 120 min.
Mix TiH2-B4Mixing the C/Cu composite powder and the CNTs suspension according to the proportion of 0.32g/ml, stirring, and stopping stirring when the upper layer solution is changed from black to transparent; standing, precipitating, pouring out the upper layer liquid, and vacuum drying the precipitate to obtain CNTs-TiH2-B4C/Cu composite powder. The vacuum drying temperature is 75 ℃, the vacuum degree is-0.06 MPa, and the drying time is 24 h.
CNTs-TiH2-B4C/Cu composite powder is filled into a steel die for cold pressing and molding, the pressing pressure is 400MPa, and the pressure maintaining time is 30 s; putting the pressed compact into a graphite die for hot-pressing sintering, wherein the sintering process comprises the following steps: heating to 800 ℃ at a heating rate of 20 ℃/min, heating to 1060 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 60min under the pressure of 28MPa, and cooling along with the furnace to obtain CNTs-TiB2-a TiC/Cu composite. The hardness was 109HBW and the conductivity was 50.95% IACS.
FIG. 2 shows TiH prepared in this example2-B4C/Cu composite powder with a flaky shape; the powder has a particle size of about 30 to 70 μm and a thickness of about 1 μm.
FIG. 3 shows CNTs-TiB prepared in this example2-the texture of TiC/Cu composite. CNTs are distributed in a strip shape, and the distribution direction of the CNTs is generally vertical to the pressurizing direction in the sintering process; TiB generated by in-situ reaction2And TiC are both granular and about hundreds of nanometers in size and are distributed among the CNTs layers.
FIG. 4 is a photograph of the high magnification structure of a portion (circled portion in white frame) of the structure of FIG. 3, wherein the structure of FIG. 3 is a strip formed by two layers of carbon nanotubes; in addition, it is notWith distributed CNTs sites, TiB of about tens of nanometers in size can also be observed2And TiC particles.

Claims (3)

1. The preparation method of the hybrid reinforced copper-based composite material is characterized by comprising the following steps:
step 1, weighing TiH2Powder of B4C powder and Cu powder, and ball milling and mixing the powder to obtain the TiH with a flaky shape2-B4C/Cu composite powder;
the TiH2Powder B4The dosage of the C powder and the Cu powder is that TiB is generated in the composite material through in-situ reaction2: 0.50-2.5 wt%, TiC: weighing the target content of 0.22-1.08 wt%;
measuring a CNTs dispersion liquid, adding deionized water to dilute the CNTs dispersion liquid into a CNTs suspension liquid, and performing ultrasonic oscillation to obtain the CNTs suspension liquid with uniformly dispersed system;
the parameters of the ball milling process are as follows: the ball milling time is 6-10 h, the ball-material ratio is 10: 1-20: 1, the rotating speed is 300-400 rpm, the addition amount of the process control agent, namely absolute ethyl alcohol, is 6-10% of the total mass of the powder, and the protective atmosphere is Ar;
step 2, the TiH obtained in the step 1 is used2-B4Adding the C/Cu composite powder into the CNTs suspension, stirring and mixing, stopping stirring when the upper layer solution is changed from black to transparent, standing, precipitating, and then drying the precipitate in vacuum to obtain CNTs-TiH2-B4C/Cu composite powder;
in the step 2, the vacuum drying temperature is 60-80 ℃, the vacuum degree is-0.06-0.05 MPa, and the drying time is 12-24 h;
step 3, the CNTs-TiH obtained in the step 22-B4Filling the C/Cu composite powder into a steel die, and performing cold pressing to form a blank; in the step 3, the pressing pressure is 300-400 MPa, and the pressure maintaining time is 20-40 s;
step 4, placing the pressed blank obtained in the step 3 into a graphite mold, and placing the graphite mold into an atmosphere hot pressing furnace for pressure sintering to obtain the CNTs-TiB2-a TiC/Cu composite;
the pressure sintering specifically comprises the following steps: in N2Under the protection of atmosphere, heating to 940-1060 ℃ at the heating rate of 10-20 ℃/min, then preserving heat for 40-80 min, increasing the pressure loaded on a pressed blank to 20-30 MPa in the heat preservation process, and then keeping unchanged;
the hybrid reinforced copper-based composite material contains three reinforcements: CNTs, TiB2And TiC, in the structure of composite material, CNTs are distributed in layer form, TiB2And TiC are dispersed in the copper matrix to form a composite structure cooperatively enhanced by three reinforcements;
the composite material comprises the following components in percentage by weight: 0.05 to 0.25 wt% of TiB2The contents are as follows: 0.50-2.5 wt% and TiC content of 0.22-1.08 wt%; the CNTs are added into the composite material through an external addition method; TiB2And TiC by TiH2And B4C is reacted and synthesized in situ in a Cu matrix.
2. The preparation method of the hybrid reinforced copper-based composite material according to claim 1, wherein the concentration of the CNTs suspension in the step 1 is 0.22-0.73 mg/ml; the ultrasonic oscillation time is 60-140 min, and the power is 40-60W.
3. The method as claimed in claim 1, wherein the step 2 is performed by TiH2-B4The mass-volume ratio of the C/Cu composite powder to the CNTs suspension is 0.29-0.44 g/ml.
CN201810266802.5A 2018-03-28 2018-03-28 Hybrid reinforced copper-based composite material and preparation method thereof Expired - Fee Related CN108384979B (en)

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